Theoretical study of ternary silver fluorides AgMF4 (M = Cu,Ni, Co) formation at pressures up to 20 GPa

Only several compounds bearing the Ag(ii) cation and other paramagnetic transition metal cations are known experimentally. Herein, we predict in silico stability and crystal structures of hypothetical ternary silver(ii) fluorides with copper, nickel and cobalt in 1 : 1 stoichiometry at a pressure range from 0 GPa up to 20 GPa employing the evolutionary algorithm in combination with DFT calculations. The calculations show that AgCoF₄ could be synthesized already at ambient conditions but this compound would host diamagnetic Ag(i) and high-spin Co(iii). Although none of the compounds bearing Ag(ii) could be preferred over binary substrates at ambient conditions, at increased pressure ternary fluorides of Ag(ii) featuring Cu(ii) and Ni(ii) could be synthesized, in the pressure windows of 7–14 and 8–15 GPa, respectively. All title compounds would be semiconducting and demonstrate magnetic ordering. Compounds featuring Ni(ii) and particularly Co(ii) should exhibit fundamental band gaps much reduced with respect to pristine AgF₂. The presence of Cu(ii) and Ni(ii) does not lead to electronic doping to AgF₂ layers, while Co(ii) tends to reduce Ag(ii) entirely to Ag(i).

Only several compounds bearing the Ag(ii) cation and other paramagnetic transition metal cations are known experimentally. Here, we predict as yet unknown AgMF₄ phases and their stability in function of pressure.     

Pseudo-octahedral nickel(ii) complexes of strongly absorbing benzannulated pincer-type amido ligands: ligand-based redox and non-Aufbau electronic behaviour

The synthesis, structures and electronic characterization of three strongly coloured, pseudo-octahedral Ni(ii) complexes supported by redox-active diarylamido ligands featuring benzannulated N-heterocyclic donor arms are reported. The S = 1 paramagnets each present two singly occupied molecular orbitals (SOMOs) identified as metal-based by density functional theory (DFT), consistent with solid-state and solution magnetism measurements. Upon applying oxidative potentials, non-Aufbau behaviour leads to the appearance of intense and well-defined absorption features extending into the near IR (NIR). The attribution of these features to the onset of aminyl radical character through ligand-based redox is corroborated by exceptionally strong intervalence charge-transfer (IVCT) transitions ascribed to electronic communication between two N_amido moieties across a Ni(ii) bridge.

The synthesis, structures and electronic characterization of three strongly coloured, pseudo-octahedral Ni(ii) complexes supported by redox-active diarylamido ligands featuring benzannulated N-heterocyclic donor arms are reported.     

Cu(ii)-thiophene-2,5-bis(amino-alcohol) mediated asymmetric Aldol reaction and Domino Knoevenagel Michael cyclization: a new highly efficient Lewis acid catalyst

The highly efficient Lewis acid-catalytic system Cu(ii)-thiophene-2,5-bis(amino-alcohol) has been developed for enantioselective Aldol reaction of isatin derivatives with ketones. The new catalytic system also proved to be highly enantioselective for the one pot three-component Domino Knoevenagel Michael cyclization reaction of substituted isatin with malononitrile and ethylacetoacetate. The chiral ligand (2S,2′S)-2,2′-((thiophene-2,5-diylbis(methylene))bis(azanediyl))bis(3-phenylpropan-1-ol) (L1) in combination with Cu(OAc)₂·H₂O employed as a new Lewis acid catalyst, furnished 3-substituted-3-hydroxyindolin-2-ones derivatives (3a–s) in good to excellent yields (81–99%) with high enantioselectivities (up to 96% ee) and spiro[4H-pyran-3,3-oxindole] derivatives (6a–l) in excellent yields (89–99%) with high ee (up to 95%). These aldol products and spiro-oxindoles constitute a core structural motif in a large number of pharmaceutically active molecules and natural products.

The highly efficient Lewis acid-catalytic system Cu(ii)-thiophene-2,5-bis(amino-alcohol) has been developed for enantioselective Aldol reaction of isatin derivatives with ketones.     

Palladium(ii)-catalyzed synthesis of indenones through the cyclization of benzenecarbaldehydes with internal alkynes

The palladium(ii)-catalyzed carbocyclization of benzenecarbaldehydes with internal alkynes to afford 2,3-disubstituted indenones was reported. The annulation reaction proceeded through the transmetalation of Pd(ii) with an aromatic aldehyde and the insertion of internal alkynes, followed by cyclization via the intramolecular nucleophilic addition of intermediate organopalladium(ii) species to the aldehyde group. This reaction proceeded in moderate to good yields with high regioselectivity.

The palladium(ii)-catalyzed carbocyclization of benzenecarbaldehydes with internal alkynes to afford 2,3-disubstituted indenones was reported.     

Extraction and preconcentration of Ni(ii), Pb(ii), and Cd(ii) ions using a nanocomposite of the type Fe3O4@SiO2@polypyrrole-polyaniline

In this study, the application of Fe₃O₄@SiO₂@polypyrrole-polyaniline magnetic nanocomposite was studied for Ni(ii), Cd(ii), and Pb(ii) ions preconcentration extraction. In this regard, the silica layer prevents the Fe₃O₄ nanoparticles (NPs) from aggregating over a broad pH range value and simultaneously improves chemical stability and hydrophilicity. By using a Box–Behnken design, the effect of various parameters affecting the preconcentration was studied. FAAS was employed to quantify the eluted analytes. The detection limits are 0.09, 1.1, and 0.3 ng mL⁻¹ for Ni(ii), Cd(ii) and Pb(ii), ions, respectively. The relative standard deviations (RSDs%) were calculated for determining the method''s precision, lower than 7.5%. The capacities of sorption are 75, 84, and 98 mg g⁻¹, respectively. With the usage of a certified reference material, the developed method was validated. After that, the validated method was employed to rapidly extract trace target ions from food samples and gave satisfactory results.

In this study, the application of Fe₃O₄@SiO₂@polypyrrole-polyaniline magnetic nanocomposite was studied for Ni(ii), Cd(ii), and Pb(ii) ions preconcentration extraction.     

Enantioselective Michael reaction of anthrone catalyzed by chiral tetraoxacalix[2]arene[2]triazine derivatives

A highly enantioselective Michael addition reaction of anthrone with nitroalkenes by chiral tetraoxacalix[2]arene[2]triazine catalysts was investigated as a novel topic. The stereoselective conversion progressed smoothly by employing 10 mol% of the catalyst and afforded the corresponding Michael adducts with acceptable to high enantioselectivities (up to 97% ee) and very high yields (up to 96%).

A highly enantioselective Michael addition reaction of anthrone with nitroalkenes by chiral tetraoxacalix[2]arene[2]triazine catalysts was investigated as a novel topic.     

Nickel(ii)-catalyzed reductive silylation of alkenyl methyl ethers for the synthesis of alkyl silanes

A new one pot protocol has been developed for the reductive silylation of alkenyl methyl ethers using Et₃Si–BPin and HSiEt₃ with nickel(ii) catalyst. Styrene type methyl ethers, multi-substituted vinyl methyl ethers, heterocycles and unconjugated vinyl ethers are all tolerated to form alkyl silanes. Mechanistic study reveals that it is a cascade of a C–O bond silylation and vinyl double bond hydrogenation process. Internal nucleophilic substitution or oxidative addition pathways were both acceptable for C–O bond cleavage. The acquired intermediate alkenyl silanes then proceeded through an unconventional reduction process thus providing alkyl silanes.

A Ni(ii)-catalyzed tandem reaction including vinyl C–O bond silylation and olefin hydrogenation has been developed providing structurally diversified alkyl silanes.     

A “turn-on” ESIPT fluorescence probe of 2-(aminocarbonyl)phenylboronic acid for the selective detection of Cu(ii)

Herein, we report a highly selective fluorescent probe for the detection of Cu(ii). The detection mechanism relies on the Cu(ii)-catalyzed oxidative hydroxylation of 2-(aminocarbonyl)phenylboronic acid into salicylamide, thus recovering the excited-state intramolecular proton transfer (ESIPT) effect and inducing more than 35-fold fluorescence enhancement. The simple structure and readily available fluorescent probe give a novel method for quantitatively detecting Cu(ii) in the linear range of 0–22 μM, with a limit of detection down to 68 nM, and exhibiting high selectivity for Cu(ii) over 16 other metal ions.

Herein, we report a highly selective fluorescent probe for the detection of Cu(ii).     

Copper(i)-catalyzed radical carboamination reaction of 8-aminoquinoline-oriented buteneamides with chloroform: synthesis of-β-lactams

A novel Cu(CH₃CN)₄PF₆-catalyzed carboamination reaction of 8-aminoquinoline-oriented buteneamides with chloroform to afford 4-(2,2,2-trichloroethyl)-β-lactams is described. The reaction proceeded at 110 °C in air with di-t-butyl peroxide. Preliminary studies indicated that the reaction undergoes a free radical mechanism via a Cu(i)/Cu(ii)/Cu(iii) catalytic cycle.

A novel Cu(CH₃CN)₄PF₆-catalyzed carboamination reaction of 8-aminoquinoline-oriented buteneamides with chloroform to afford 4-(2,2,2-trichloroethyl)-β-lactams is described.     

Synthesis and characterization of a surface-grafted Pb(ii)-imprinted polymer based on activated carbon for selective separation and pre-concentration of Pb(ii) ions from environmental water samples

Even the lowest concentration level of lead (Pb) in the human body is dangerous to health due to its bioaccumulation and high toxicity. Therefore, it is very important to develop selective and fast adsorption methods for the removal of Pb(ii) from various samples. In this paper, a new Pb(ii) ion-imprinted polymer (Pb(ii)-IIP) was prepared with surface imprinting technology by using lead nitrate as a template, for the solid-phase extraction of trace Pb(ii) ions in environmental water samples. The imprinted polymer was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy and N₂ adsorption–desorption isotherms. The separation/pre-concentration conditions for Pb(ii) were investigated, including the effects of pH, shaking time, sample flow rate, elution conditions and interfering ions. Compared with non-imprinted particles, the ion-imprinted polymer had a higher selectivity and adsorption capacity for Pb(ii). The pseudo-second-order kinetics model and Langmuir isotherm model fitted well with the adsorption data. The relative selectivity factor values (α_r) of Pb(ii)/Zn(ii), Pb(ii)/Ni(ii), Pb(ii)/Co(ii) and Pb(ii)/Cu(ii) were 168.20, 192.71, 126.13 and 229.39, respectively, which were all much greater than 1. The prepared Pb(ii)-imprinted polymer was shown to be promising for the separation/pre-concentration of trace Pb(ii) from natural water samples. The adsorption and desorption mechanisms were also proposed.

Even the lowest concentration level of lead (Pb) in the human body is dangerous to health due to its bioaccumulation and high toxicity.     

Regio-selective and stereo-selective hydrosilylation of internal alkynes catalyzed by ruthenium complexes

In this study, ruthenium(ii)-catalyzed direct hydrosilylation of internal alkynes with high regio-selectivity and stereo-selectivity is reported. This title transformation led to various vinylsilanes in good to excellent yields. This approach features mild reaction conditions, low catalyst loading, air-stability, and good functional group tolerance. Furthermore, gram-scale preparation and some transformations of vinylsilanes were carried out, which further underscored its synthetic utility and applicability.

In this study, ruthenium(ii)-catalyzed direct hydrosilylation of internal alkynes with high regio-selectivity and stereo-selectivity is reported.     

Removal of Pb(ii) and Cr(vi) from aqueous solutions using the prepared porous adsorbent-supported Fe/Ni nanoparticles

In this study, Fe/Ni nanoparticles supported by a novel fly ash-based porous adsorbent (FBA-Fe/Ni) for Cr(vi) and Pb(ii) removal were investigated. In order to enhance the reactivity of zero-valent iron (ZVI), ZVI particles were deposited on the surface or in the inner pores of FBA as a support material and Ni nanoparticles were introduced. FBA was prepared with the solid waste such as Enteromorpha prolifera, bentonite and fly ash. FBA-Fe/Ni was characterized via Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction and the Brunauer–Emmett–Teller model and energy-dispersive spectrometry. The effects of various parameters on Cr(vi) and Pb(ii) removal by FBA-Fe/Ni, such as FBA-Fe/Ni dosage, pH of the solution, reaction temperature, Cr(vi) and Pb(ii) concentrations, co-existing ions and ionic strength were discussed. The possible removal mechanisms were proposed and the results indicated that there was a three-step reaction including the adsorption of Cr(vi) and Pb(ii) on the surface of FBA-Fe/Ni, the subsequent reduction and precipitation. The removal capacity of Cr(vi) and Pb(ii) by FBA-Fe/Ni was 25.07 mg g⁻¹ and 164.19 mg g⁻¹ at 303 K with an initial concentration of 1000 mg L⁻¹ and FBA-Fe/Ni dosage of 0.20 g. In conclusion, this work demonstrated that FBA-Fe/Ni was a promising alternative material for Cr(vi) and Pb(ii) removal.

In this study, Fe/Ni nanoparticles supported by a novel fly ash-based porous adsorbent (FBA-Fe/Ni) for Cr(vi) and Pb(ii) removal were investigated.     

Ni(ii)-catalyzed mono-selective ortho-arylation of unactivated aryl C–H bonds utilizing amino acids as a directing group

The nickel(ii)-catalyzed ortho-arylation of unactivated C–H bonds utilizing amino acids as directing groups with aryl iodides or bromides as coupling electrophiles is described. This protocol features excellent mono-selectivity, good regioselectivity, and wide functional group tolerance. Additionally, the obtained products bearing a biaryl motif and an amino acid represent bioactive molecules with wide bioactivities.

The nickel(ii)-catalyzed ortho-arylation of unactivated C–H bonds utilizing amino acids as directing groups with aryl iodides or bromides as coupling electrophiles is described.     

Unraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles

A theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP⁻) catalyzed by Zn(ii)-complexes featuring uncoordinated nucleophiles. Ligand-based and alternative solvent-based nucleophilic attack reaction models are proposed. The pK_a values of the Zn(ii)-bound water molecules or ligands in the [Zn(LⁿH)(η-H₂O)(H₂O)]²⁺ (n = 1, 2 and 3) complexes, as well as the dimerization tendency of the mononuclear Zn(ii)-complexes, were found to significantly influence the reaction mechanisms. The Zn(ii)-L³ complexes were found to be more favorable for the hydrolytic cleavage of the BNPP⁻via a ligand-based nucleophilic attack pathway. This was due to the lower pK_a value for the deprotonation of the oxime ligand, the hard dimerization of the mononuclear Zn(ii)-L³ species, and the presence of an uncoordinated nucleophile. The origins of the uncoordinated reactions were systematically elucidated. The theoretical results reported here are in good agreement with experimental observations and more importantly, help to elucidate the factors that influence intermolecular nucleophilic attack reactions with coordinated/uncoordinated nucleophiles.

A theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP⁻) catalyzed by Zn(ii)-complexes featuring uncoordinated nucleophiles.     

Synthesis,characterization and cytotoxicity evaluation of a novel magnetic nanocomposite with iron oxide deposited on cellulose nanofibers with nickel (Fe3O4@NFC@ONSM-Ni)

A heterogeneous, magnetically recoverable nanocomposite, Fe₃O₄@NFC@ONSM-Ni(ii) was prepared by immobilization of a novel Ni(ii) Schiff base complex on Fe₃O₄@NFC nanoparticles followed by treatment with melamine. This trinuclear catalyst has been characterized using several analytical techniques including FT-IR, TEM, Fe-SEM, EDX, DLS, ICP, TGA, VSM, and XRD. It was used as an efficient catalyst for one-pot solvent-free synthesis of 1,4-dihydropyridine and poly-hydro quinoline derivatives through Hantzsch reaction. This catalyst showed remarkable advantage over previously reported catalysts due to suitable conditions, short reaction time, high efficiency and lower catalyst load and timely recovery of the magnetic catalyst. Moreover, the effects of Fe₃O₄@NFC@ONSM-Ni(ii) nanoparticles on the in vitro proliferation of human leukemia cell line (k562) and human breast cancer cells (MDA-MB-231) were investigated. The results of MTT and Hochest assays suggested that the nanoparticles could effectively inhibit the proliferation of these cancer cells in a time- and concentration-dependent manner.

A heterogeneous, magnetically recoverable nanocomposite, Fe₃O₄@NFC@ONSM-Ni(ii) was prepared by immobilization of a novel Ni(ii) Schiff base complex on Fe₃O₄@NFC nanoparticles followed by treatment with melamine.     

Cd(ii) removal by Fe(ii) surface chemically modified layered double hydroxide–graphene oxide: performance and mechanism

Cd(ii) adsorption onto Fe(ii) modified Layered double hydroxide–graphene oxide (LDH–GO@Fe(ii)) was investigated using batch experiments. With the modification of Fe(ii), LDH–GO maintained its structure, while Fe(ii) species formed non-crystalline iron oxide clusters on the surface of the LDH/GO. A kinetics study indicated that adsorption obeyed a pseudo-second-order rate law. The equilibrium data were fitted well with the Langmuir isotherm model. The maximum adsorption capacity of LDH–GO@Fe(ii)₁₀ was 28.98 mg g⁻¹, higher those that of pure LDH–GO and LDH–GO@Fe(ii)₅₀. The increased sorption capacities could be explained by the increased specific surface area. Modification with Fe(ii) would lead to the generation of amorphous Fe oxides and Fe could occupy the binding sites for Cd(ii), thus excess Fe in the structure will restrain the adsorption of Cd(ii). The XRD and XPS patterns revealed the formation of Cd(OH)₂ after adsorption. Batch experiments indicated that precipitation and surface complexation were the main pathways for Cd(ii) removal.

Fe(ii)-decorated LDH–GO composites had a high capacity for Cd(ii) removal. The mechanisms were controlled by surface-induced precipitation and complex formation.     

Mimicking 2,2′:6′,2′′:6′′,2′′′-quaterpyridine complexes for the light-driven hydrogen evolution reaction: synthesis,structural, thermal and physicochemical characterizations

The synthetic difficulties associated with quaterpyridine (qtpy) complexes have limited their use in the formation of various metallosupramolecular architectures in spite of their diverse structural and physicochemical properties. Providing a new facile synthetic route to the synthesis of functionalised qtpy mimics, we herein report the synthesis of three novel –NH₂ functionalized qtpy-like complexes 12–14 with the general formula M(C₁₆H₁₄N₁₂)(NO₃)₂ (M = Co(ii), Ni(ii) and Cu(ii)) in high yield and purity. Characterization of these complexes has been done by single crystal X-ray diffraction (SCXRD), thermogravimetric analysis, UV-Vis, infrared, mass spectrometry and cyclic voltammetry. As indicated by SCXRD, in all the synthesized complexes, the metal ions show a strongly distorted octahedral coordination geometry and typical hydrogen bonding networks involving DAT groups. In addition, complexes 12–14 have been analyzed as potential photocatalysts for hydrogen evolution reaction (HER) displaying good turnover numbers (TONs). Hydrogen produced from these photocatalysts can serve as the possible alternative for fossil fuels. To the best of our knowledge, this is the only study showcasing –NH₂ functionalized qtpy-like complexes of Co(ii), Ni(ii) and Cu(ii) and employing them as photocatalysts for HER. Thus, a single proposed strategy solves two purposes-one related to synthesis while second is related to our environment.

Facile synthesis of three novel –NH₂ functionalized qtpy-like complexes, their characterizations and study of their photocatalytic properties for hydrogen evolution reaction.     

Selective removal of lead ions from aqueous solutions using 1,8-dihydroxyanthraquinone (DHAQ) functionalized graphene oxide; isotherm,kinetic and thermodynamic studies

An anthraquinone – graphene structure was fabricated and applied for the removal of lead(ii) from aqueous solution. The equilibrium occurred in about 10 min revealing the high adsorption rate at the beginning of the process. The maximum Pb(ii) adsorption capacity of the Fe₃O₄@DHAQ_GO nanocomposite was about 283.5 mg g⁻¹ that was observed at 323 K and pH 5.5. The Pb(ii) adsorption ability increased with the increasing pH. The isotherm and kinetic studies indicated that the Sips isotherm model and the linear form of the pseudo-second kinetic model had a better fit with the experimental results. The positive value of ΔH⁰ indicated endothermic interactions between Pb(ii) and Fe₃O₄@DHAQ_GO. The negative ΔG⁰ indicated that the reactions are spontaneous with a high affinity for Pb(ii). The positive ΔS⁰ values indicated increasing randomness at the solid–solute interface during the adsorption process. The selective removal of Pb(ii) by the nanocomposite confirms the presence of higher-affinity binding sites for Pb(ii) than Cd(ii), Co(ii), Zn(ii), and Ni(ii) ions. Furthermore, the Fe₃O₄@DHAQ_GO nanocomposite revealed an excellent preferential adsorbent for Pb(ii) spiked in drinking water samples containing natural ion matrices. EDTA-2NA 0.01 N was found to be a better elution agent than HCl 0.1 M for the nanocomposite regeneration. After five adsorption/desorption cycles using EDTA-2NA 0.01 N, more than 84% of the adsorbed Pb(ii) was still desorbed in 30 min. Capturing sub-ppm initial concentrations of Pb(ii) and the capability to selectively remove lead from drinking water samples make the Fe₃O₄@DHAQ_GO nanocomposite practically convenient for water treatment purposes. High adsorption capacity and facile chemical synthesis route are the other advancements.

The Fe₃O₄@DHAQ_GO nanocomposite can serve as an efficient adsorbent for the selective removal of lead from polluted water.     

Comparative study of Ni(ii) adsorption by pristine and oxidized multi-walled N-doped carbon nanotubes

The principles and mechanisms of adsorption of Ni(ii) ions by well characterized pristine and oxidized N-doped multi-walled carbon nanotubes (N-CNTs) are described and discussed. The samples were synthesized by CCVD method using n-butylamine as the carbon source and Ni(NO₃)₂ + MgO as the catalyst and purified by treatment with HCl. The surface functionalization was performed using oxidation with a mixture of concentrated H₂SO₄ and HNO₃. The morphology, nature and charge of surface groups were characterized by HRTEM, XPS, FTIR and micro-electrophoresis methods. It has been shown that: adsorption of Ni(ii) reaches an equilibrium value within 20–30 min; the degree of extraction of nickel ions from the solution increases with its dilution; adsorption of Ni(ii) results in an insufficient decrease in the suspension pH for pristine N-CNTs (0.5–0.6 pH unit) and considerable lowering of the pH for the oxidized sample (up to 2.5 pH unit); the adsorption isotherms are described by the Langmuir equation; the plateau amounts of adsorption (35–40 mg g⁻¹) are almost the same for both as-prepared and oxidized samples; at pH 8 and higher a sharp increase in adsorption is observed which is caused by nickel hydroxide precipitation. The spectroscopic, adsorption, electrophoretic and pH measurement data testify that below pH 8 the major mechanism of adsorption by as-prepared N-CNTs is the donor–acceptor interaction between the free electron pair of N atoms incorporated into the nanotube lattice and vacant d-orbital of the adsorbing Ni(ii) ions. For the oxidized N-CNTs ion-exchange processes with a release of H⁺ play a decisive role.

The principles and mechanisms of adsorption of Ni(ii) ions by well characterized pristine and oxidized N-doped multi-walled carbon nanotubes (N-CNTs) are described and discussed.     

Cu(ii) vitamin C tunes photocatalytic activity of TiO2 nanoparticles for visible light-driven aerobic oxidation of benzylic alcohols

The incorporation of Cu(OAc)₂ into ascorbic acid coated TiO₂ nanoparticles easily provided a new heterogeneous visible-light active titania-based photocatalyst (TiO₂-AA-Cu(ii)) which was characterized by different techniques such as FT-IR, XPS, ICP-AES, TGA and TEM. A red-shift of the band-edge and a reduction of the band-gap (2.8 eV vs. 3.08 for TiO₂) were demonstrated by UV-DRS and Tauc plots. The combination of the as-prepared TiO₂-AA-Cu(ii) nanoparticles with TEMPO and molecular oxygen (air) afforded an active catalytic system for the selective oxidation of diverse set of benzylic alcohols under solvent-free conditions. A photoassisted pathway was confirmed for oxidation reactions evidenced by good correlation between apparent quantum yield (AQY) and diffuse reflectance spectra (DRS) of the as-prepared nanohybrid. The spectral data and recycling experiments demonstrated the structural stability of the title copper photocatalyst during oxidation reactions.

The combination of TiO₂-AA-Cu(ii) nanoparticles with TEMPO and molecular oxygen (air) afforded an active catalytic system for the selective oxidation of diverse set of benzylic alcohols under solvent-free condition.